The present invention relates to new chemical entities and the incorporation and use of the new chemical entities as fragrance chemicals.
U.S. Pat. Nos. 5,227,367; 5,733,866; and 5,665,698 hereby incorporated by reference as iset forth in their entirety disclose polycyclic chemicals that are suitable for use as fragrance chemicals. Those with skill in the art appreciate how differences in the chemical structure of the molecule can result in significant differences in the odor, notes and characteristics of a molecule. These variations and the ongoing need to discover and use the new chemicals in the development of new fragrances allows perfumers to apply the new compounds in creating new fragrances.
The present invention provides novel chemicals, and the use of the chemicals to enhance the fragrance of perfumes, toilet waters, colognes, personal products and the like. In addition, the present invention is directed to the use of the novel chemicals to enhance fragrance in perfumes, toilet waters, colognes, personal products and the like.
More specifically, the present invention is directed to the novel compounds, represented by the structure of Formula I set forth below: 
where A is 
B is 
or A and B together form the ring structure 
and X, Rxe2x80x2 and R are independently H and CH3 and m=0 or 1.
Another embodiment of the invention is a method for enhancing a fragrance by incorporating an olfactory acceptable amount of the compound provided above.
These and other embodiments of the present invention will be apparent by reading the following specification.
The novel compounds of the present invention are more fully described by the following structures: 
where X, A, and B are as described above.
Those with skill in the art will appreciate that the dotted line represents a single or double bond. In a preferred embodiment the molecule does not contain a double bond. In a highly preferred embodiment the molecules contain the ring structure without the double bond and m=0. These molecules are represented by the following structure: 
where A, B and X have the definition set forth above. In a preferred embodiment of the invention the compounds have the following structure 
Most preferably M=0 and R and Rxe2x80x2 are independently selected from H and CH3.
Highly preferred embodiments of the invention are the following compounds wherein the substituents have the following values when applied to the compound of Formula I:
The novel compounds of the present invention are prepared by one of several reaction sequences set forth below. The compounds of Examples 1, 2, 3, 8, 9, 10, 12, 13, and 14, set forth below, were prepared by the sequence: 
The reaction sequence set forth above is summarized by the following reactions. The first reaction is a three (3) carbon addition via allyl alcohol Claisen rearrangement or carbon alkylation with methallyl chloride. This reaction (Claisen rearrangement) is typically conducted at a temperature of from about 150 to about 250xc2x0 C. In a preferred embodiment the reaction is catalyzed using an acid catalyst, preferably methanesulfonic acid or para toluenesulfonic acid. The carbon addition reaction is then followed by an aluminum hydride ketone reduction reaction. The ketone is reduced to form the corresponding alcohol. The final reaction set forth above is an acid catalyzed ether formation that is conducted at a temperature of from about 70 to about 130xc2x0 C. This reaction is usually conducted in a solvent such as xylene or toluene with toluene being the preferred solvent.
The compounds of Examples 5-7 were prepared by the following general sequence: 
The first reaction is a carbon alkylation employing either allyl chloride or methallyl chloride depending if the desired R group is H or CH3. This reaction is typically conducted at a temperature of from about 23 to about 100xc2x0 C. The reaction is usually conducted with a base catalyst employing sodium methoxide or sodium hydroxide. The next reaction is a thermal Claisen rearrangement conducted at a temperature of from about 170 to about 250xc2x0 C. The third reaction is an acid catalyzed ether formation employing similar temperatures and catalysts as described above, followed by a catalytic hydrogenation employing rhodium or platinum as a catalyst.
The compounds of Examples 4 and 11 are prepared by the sequence: 
wherein the reaction is a three (3) carbon addition via allyl alcohol Claisan rearrangement or carbon alkylation with methallyl chloride using the conditions and catalysts described above.
The starting materials when M=0 for the above described reaction can be found in U.S. Pat. Nos. 5,227,367, 5,733,866 and 5,665,698. Similarly, the starting materials for the above materials when M=1 can be found in U.S. Pat. No. 3,927,083, hereby incorporated by reference, German patent 2330648 and Japanese patent 09249584.
Those with skill in the art will recognize that the compounds of the present invention have several chiral centers, thereby providing numerous isomers of the claimed compounds. As used herein the compounds described herein include the isomeric mixtures of the compounds as well as those isomers that may be separated using techniques known to those with skill in the art. Suitable techniques include chromatography, particlularly gel chromatography.
The optical isomers for the compound 4,10,10,11,12,12-hexamethyl-3-oxatricyclo[7.3.0.0 less than 2,6 greater than ]dodecane are provided in the following table. One with skill in the art would be able to formulate fragrance compositions using one or more or the following isomers and mixtures of the isomers:
The compounds of the present invention have a powerful amber fragrance, with soft, woody notes.
The use of the compounds of the present invention is widely applicable in current perfumery products, including the preparation of perfumes and colognes, the perfuming of personal care products such as soaps, shower gels, and hair care products as well as air fresheners and cosmetic preparations. The present invention can also be used to perfume cleaning agents, such as, but not limited to detergents, dishwashing materials, scrubbing compositions, window cleaners and the like.
In these preparations, the compounds of the present invention can be used alone or in combination with other perfuming compositions, solvents, adjuvants and the like. The nature and variety of the other ingredients that can also be employed are known to those with skill in the art.
Many types of fragrances can be employed in the present invention, the only limitation being the compatibility with the other components being employed. Suitable fragrances include but are not limited to fruits such as almond, apple, cherry, grape, pear, pineapple, orange, strawberry, raspberry; musk, flower scents such as lavender-like, rose-like, iris-like, carnation-like. Other pleasant scents include herbal and woodland scents derived from pine, spruce and other forest smells. Fragrances may also be derived from various oils, such as essential oils, or from plant materials such as peppermint, spearmint and the like.
A list of suitable fragrances is provided in U.S. Pat. No. 4,534,891, the contents of which are incorporated by reference as if set forth in its entirety. Another source of suitable fragrances is found in Perfumes Cosmetics and Soaps, Second Edition, edited by W. A. Poucher, 1959. Among the fragrances provided in this treatise are acacia, cassie, chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle, hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cut hay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose, vanilla, violet, wallflower, and the like.
Olfactory effective amount is understood to mean the amount of compound in perfume compositions the individual component will contribute to its particular olfactory characteristics, but the olfactory effect of the perfume composition will be the sum of the effects of each of the perfumes or fragrance ingredients. Thus the compounds of the invention can be used to alter the aroma characteristics of the perfume composition, or by modifying the olfactory reaction contributed by another ingredient in the composition. The amount will vary depending on many factors including other ingredients, their relative amounts and the effect that is desired.
The level of compound of the invention employed in the fragranced article varies from about 0.005 to about 10 weight percent, preferably from about 0.5 to about 8 and most preferably from about 1 to about 7 weight percent. In addition to the compounds other agents can be used in conjunction with the fragrance. Well known materials such as surfactants, emulsifiers, polymers to encapsulate the fragrance can also be employed without departing from the scope of the present invention.
Another method of reporting the level of the compounds of the invention in the perfumed composition, i.e., the compounds as a weight percentage of the materials added to impart the desired fragrance. The compounds of the invention can range widely from 0.005 to about 70 weight percent of the perfumed composition, preferably from about 0.1 to about 50 and most preferably from about 0.2 to about 25 weight percent. Those with skill in the art will be able to employ the desired level of the compounds of the invention to provide the desired fragrance and intensity.
The following are provided as specific embodiments of the present invention. Other modifications of this invention will be readily apparent to those skilled in the art. Such modifications are understood to be within the scope of this invention. As used herein all percentages are weight percent unless otherwise noted, ppm is understood to mean parts per million; mm is understood to be millimeters, ml is understood to be milliliters, Bp is understood to be boiling point, THF is understood to be tetrahydrofuran, Hg is understood to be mercury and g is understood to be grams. IFF as used in the examples is understood to mean International Flavors and Fragrances Inc., Hazlet, N.J., USA.